CN103015155A - Method for improving tensile strength of carbon fiber - Google Patents
Method for improving tensile strength of carbon fiber Download PDFInfo
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- CN103015155A CN103015155A CN2012105067051A CN201210506705A CN103015155A CN 103015155 A CN103015155 A CN 103015155A CN 2012105067051 A CN2012105067051 A CN 2012105067051A CN 201210506705 A CN201210506705 A CN 201210506705A CN 103015155 A CN103015155 A CN 103015155A
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Abstract
The invention relates to a method for improving the tensile strength of a carbon fiber. An improved electric atomization deposition method is adopted for planting carbon nano tubes into surface structure defects of the carbon fiber, so as to improve the strength of the carbon fiber. The method provided by the invention comprises the following steps of: 1) transmitting a pre-oxidized and carbonized carbon fiber bundle into a high-voltage corona discharge area, and carrying out corona discharge under a high voltage of minus 5kV to minus 30kV, wherein the advancing speed is 5-30m/h, so that a certain amount of negative charge is taken along in the surface structure defects of the carbon fiber; 2) preparing the carbon nano tubes and an organic solvent into a uniform and stable suspension, wherein each carbon nano tube is a single-walled carbon nano tube or a multi-walled carbon nano tube, and the organic solvent is one of dimethylacetamide, dimethylformamide, tetrahydrofuran and ethanol organic solvent; 3) applying positive static electricity of 20-50kV to the carbon nano tube suspension, flattening the charged carbon fiber bundle and grounding to form a suspension acceptor, and then planting the carbon nano tubes into the surface structure defects of the carbon fiber by virtue of electric atomization deposition, wherein deposit is controlled to be 1000:(0.1-4) in weight ratio of the carbon fiber to the carbon nano tubes; and 4) carrying out heat treatment on the carbon fiber bundle under the insert gas argon atmosphere at the temperature of 300-1600 DEG C after atomization deposition is carried out by virtue of the carbon nano tubes. The tensile strength of the carbon fiber can be improved by more than 110%.
Description
Technical field
The present invention relates to a kind of method that improves tensile strength of carbon fibers, particularly adopt the method that the electrospray sedimentation is repaired the carbon fiber surface fault of construction with CNT and then improved tensile strength of carbon fibers of improving.
Background technology
Carbon fiber almost can be considered to up to now specific strength and the highest nonmetallic materials of specific modulus, except the mechanical property of excellence, it also has other multiple premium properties concurrently,, resist chemical high temperature resistant such as low-density, low resistance, high thermal conductance, low-thermal-expansion, radiation hardness etc., become the reinforcing material of the indispensable advanced composite material of aerospace field, also had wide practical use in fields such as communications and transportation, the energy, athletic sports appliance, civil construction.Yet in fact the intensity of existing carbon fiber product and elastic modelling quantity exist very large gap with theoretical value, take TENSILE STRENGTH as example, only are 3～5% of theoretical value generally.The basic reason that causes this phenomenon is carbon fiber ubiquity fault of construction, carbon fiber such as acrylonitrile group prepares with solution spinning because of its precursor especially, fiber is followed the effusion of solvent in solidification forming, the carbon fiber structural defective that finally makes is particularly serious.The fault of construction of carbon fiber comprises internal flaw (such as the cavity) and blemish (such as depression and crackle), and blemish is the principal element that causes intensity to descend, its weight even can reach 90%.
In the prior art, people more pass through to improve former yarn quality, improve pre-oxidation and carbonization technique etc. in the hope of the formation of minimizing fault of construction, but produce little effect with regard to the improvement ratio of carbon fiber product intensity actual value and theoretical value gap." Nanotube composite carbon fibers " [" Applied Physics Letters " 1999,75 (7), P1329～1334] literary composition discloses a kind of co-blended spinning method that adopts Single Walled Carbon Nanotube sneaked into the method that precursor prepares asphalt base carbon fiber, to improve mechanical property and the electrical property of carbon fiber, it is said that the asphaltic base carbon fiber reinforce plastic TENSILE STRENGTH and the elastic modelling quantity that contain the 5wt.% Single Walled Carbon Nanotube have improved respectively 90% and 150%.Yet the method has mainly remedied carbon fiber internal structure defective, the Surface Structures defective remedy the effect limited.In addition, the surface energy of CNT is very big, be scattered in equably in the spinning solution by no means easyly, uses so be difficult to realize large-scale industrialization.The in addition also trial of visible " later stage reparation " discloses a kind of manufacture method of high-strength carbon fiber such as Chinese patent application 03137023.3, and it is with CH
4Pass into plasma generator with Ar with certain proportioning, satisfy carbon fiber by the plasma high-temperature district, carry out the graphited while at carbon fiber, methane cracking under the effect of high-temperature electric arc plasma produces the carburizing of ion carbon to carbon fiber surface and inside, thereby remedies its fault of construction.The good news is that very it is stronger to the specific aim of carbon fiber surface fault of construction reparation, but " reparation " efficient of obvious this method is not ideal enough, the cost of industrial applications can be higher.Cheng Bowen etc. disclose the intensity that a kind of method that adopts the electrostatic spraying CNT increases carbon fiber in Chinese patent application numbers 201010211436.7,201010211437.1,201010211410.2 etc., the method technique is simple, and carbon fiber strength improves more than 100%.But this technology Shortcomings is: only have the part CNT to enter in the surface texture defective of carbon fiber (radially injecting) in the electrostatic spray process, most CNTs cover carbon fiber surface, and impact strengthens effect.
Summary of the invention
The invention provides a kind of method that improves tensile strength of carbon fibers, it repairs the carbon fiber surface fault of construction after having adopted CNT, and then increases the intensity of carbon fiber.Effect and efficient are all very good, are suitable for industrializing implementation, have solved preferably the technical problem that prior art exists, and greatly reduce simultaneously the consumption of CNT.
Below be the concrete technical scheme of the present invention:
A kind of method that improves tensile strength of carbon fibers, it adopts improvement electrospray sedimentation that CNT is implanted in the surface texture defective of carbon fiber and then increases its intensity.The method comprises following process:
1) carbon fiber Corona discharge Treatment: the carbon fiber bundle 1 after pre-oxidation, the charing is sent to the high-voltage corona discharge district by conveyer belt 6 carries out Corona discharge Treatment, corona discharge assembly comprises that high voltage source 2, point discharge device 3 and grounding electrode plate 4 form, wherein high voltage source 2 is the negative electricity generator, its negative pole links to each other with point discharge device 3 by wire 21, and is anodal by wire 22 ground connection; By the gait of march 5～30m/h of control conveyer belt 6, the corona voltage of high voltage source 2-5～-30kV, arcing distance (point discharge device 3 and grounding electrode plate 4 spacings) is 1～5cm;
2) carbon nano tube suspension configuration: CNT and organic solvent are mixed with stable homogeneous suspension, organic solvent is a kind of in dimethylacetylamide, dimethyl formamide, oxolane or the ethanol, and the content of CNT is 10～60g/L in the suspension;
3) electrostatic precipitation CNT: the carbon fiber bundle 1 through Corona discharge Treatment enters the electrostatic precipitation district through conveyer belt 6 with identical speed, the electrostatic precipitation device is comprised of high voltage source 7, spininess injector 9 and grounding electrode plate 4 ', high voltage source 7 is positive electric generator, its anodal wire 71 that passes through links to each other with spininess injector 9, and negative pole is by wire 72 ground connection; Carbon nano tube suspension is delivered to spininess injector 9 cavitys that are positioned at directly over the carbon fiber 1 through conduit 8, high voltage source 7 applies voltage 20～50kV and forms the electro-deposition district with grounding electrode plate 4 ', carbon fibre tow 1 lies on conveyer belt 6 and consists of acceptor, carbon nano tube suspension is deposited on CNT in the carbon fiber surface in the surface texture defective by electrostatic atomization, obtains CNT and repairs carbon fiber; Deposition distance (distance between injector syringe needle and the carbon fiber bundle) is controlled to be 5～30cm, and in the weight ratio of carbon fiber and CNT, the deposition of CNT is controlled to be 1000 on the carbon fiber: (0.1～4);
4) CNT is repaired carbon fiber heat treatment: carbon fiber bundle is delivered in the annealing device 11 with identical speed behind the CNT spray deposition, under inert gas argon gas atmosphere, heat-treat, 300～1600 ℃ of heat treatment temperatures, carbon fiber speed is passed through annealing device.
Said process 1) is actually at carbon fiber surface and introduces as a result some negative electrical charges in the defective, will help like this to be implanted in the carbon fiber surface fault of construction with the carbon nano-tube oriented of positive charge, but not be deposited on the surface of carbon fiber.Its basic principle is: under the high-pressure electrostatic effect, pin termination electrode 3 changes into air pole just, negative two kinds of electric charges, the positive charge opposite with electrode moves towards the needlepoint electrode end, and the negative electrical charge identical with polarity of electrode is deposited on the surface of carbon fiber and carbon fiber, because the carbon fiber guiding electrical property is better, the electric charge that is deposited on carbon fiber surface forms easily the conductive channel loss and disappears, but the electric charge in the defective is difficult to be formed the loss passage and resides in the fault of construction, thus reside in the fault of construction the negative electrical charge electric charge will with electrospray deposition process subsequently in attract each other so that in the easier surface texture defective that enters carbon fiber of CNT with the CNT of positive charge.Preferred 50～the 70cm/min of gait of march of the conveyer belt 6 described in this process, the corona voltage of described high voltage source 2-20～-25kV, described arcing distance is 2～3cm.This process can Effective Regulation electrospray deposition process in the directed movement of particle, it is better to compare traditional electrical spray deposition implementation result.
Said process 2) described CNT can be Single Walled Carbon Nanotube and/or multi-walled carbon nano-tubes, and the diameter of Single Walled Carbon Nanotube is distributed as 0.5～5nm, and the diameter of multi-walled carbon nano-tubes is distributed as 10～20nm, and distribution of lengths is 5～10 μ m; Described solvent is a kind of in dimethylacetylamide, dimethyl formamide, oxolane or the ethanol organic solvent; The content of CNT is preferably 30～40g/L in the described suspension.
Said process 3) described spininess injector 9 preferably applies the anodal static of 30～40kV; Described deposition distance preferably is controlled to be 15～25cm; The deposition of CNT preferably is controlled to be 1000 on the described carbon fiber: (1.5～2.5).
Said process 4) effect is to make carbon fiber and CNT at the interface, the active atoms of carbon of CNT active atoms of carbon in the carbon fiber surface fault of construction is combined, so that form covalent bonds between carbon fiber and CNT, to improve the carbon fiber mechanical property; When treatment temperature enough high, except above-mentioned covalent bonds occurs, carbon fiber structural changes the higher graphite-structure of degree of crystallinity into from random graphits structure, crystallization will occur between turbostratic graphite and the layered carbon nano pipe to reset simultaneously, whole process comprises the processes such as the eliminating, multinuclear aromatic ring plane structural organization, crystallite rearrangement, crystallite merging of non-carbon atom, will can further improve tensile strength of carbon fibers and modulus like this.But consider that temperature is higher, equipment requirement is also strict, and processing cost will significantly increase, preferred 1000～1300 ℃ of the heat treatment temperature described in the present invention.
One of key problem in technology of the present invention is that this desirable high-carbon reinforcing material of selection CNT is implemented the reparation to the carbon fiber surface fault of construction.It is generally acknowledged when carbon fiber is subject to External Force Acting, the easiest breakaway poing that becomes fiber of the crackle of fiber surface, under external force, the tip of crackle will produce stress and concentrate, owing to lack plastic deformation, the stress of concentrating is difficult for relaxing and discharges, and can only form new surface with crackle bamboo telegraph and expansion, finally causes the carbon fiber fracture.The diameter of CNT is nanoscale (a few nanometer), and far below the carbon fiber surface crack size, under electrostatic atomization deposition electric field action, CNT is very easy to be filled in the crackle.Specific area is large, surface energy is high, surface atom proportion high because CNT has, intermolecular force between CNT and CNT, CNT and the carbon fiber (Van der Waals force) is high, particularly after heat treatment also has covalent bond between the carbon atom in CNT and the carbon fiber structural defective.For this reason, the load of carbon fiber crackle one side after the CNT reparation can be fast be passed to the opposite side of crackle by being filled in CNT in the crackle, and then stress that can the establishment cracks concentrates, and realizes that its tensile strength improves.
Yet, just because the surface energy of CNT is larger, very easily gather, thus CNT before the electrospray deposition self Uniform Dispersion and orientated deposition to be implanted in the carbon fiber surface fault of construction be the prerequisite that reaches above-mentioned desirable reparation state necessity.Another key problem in technology of the present invention is to utilize dexterously the improvement electrospray to deposit this technological means, and determines suitable sedimentary condition as the basis take a large amount of experiments, thereby has successfully realized above-mentioned target.After the suspension that contains CNT has applied high-voltage positive electrode static, because of CNT band like charges, thereby mutually repel and be vaporific dispersion with dispersion liquid, the at this moment volatilization of solvent, the positively charged CNT of separating out be directed the implantation in the carbon fiber surface fault of construction under the effect of electrostatic field force.Suitable deposition is very important, the very few effect that is difficult to manifest enhancing, and the excessive humidification that then can not give play to CNT fully increases cost.
Although the thickness of single wall or multi-walled carbon nano-tubes is different, but its difference still belongs to very small for the size of carbon fiber surface fault of construction after all, simultaneously this species diversity is unlikely to cause the condition of repair process to change to some extent, so no matter the CNT of single wall or many walls uses separately or both use with the mixing of any ratio and all do not affect realization of the present invention.Just because the active atoms of carbon of Single Walled Carbon Nanotube is more, and is easier to tangle and produces more network node, experimental data shows that the usage ratio when Single Walled Carbon Nanotube increases, and strengthening effect can improve thereupon.
The tensile strength of carbon fiber can improve more than 110% after the CNT reparation of the present invention, and has the advantages such as technique is simple, the CNT consumption is few, cost is low, efficient is high, the repairing effect of carbon fiber surface fault of construction is good, is easy to realize industrial applications.
[0019] description of drawings
Fig. 1 is that the present invention adopts improvement electrospray sedimentation that CNT is implanted carbon fiber surface fault of construction schematic diagram.
The below will the invention will be further described by specific embodiment.
The specific embodiment
[embodiment 1～7]
(1) carbon fiber Corona discharge Treatment
Adopt self-control to test without the PAN base carbon fibre of gluing, the specification of carbon fiber is: 3K, single fiber average diameter 7.0 μ m.Carbon fibre tow 1 is launched, and be tiled in stainless conveyer belt 6 and deliver to the high-voltage corona discharge district and carry out Corona discharge Treatment, by controlling the gait of march of suitable conveyer belt 6, the corona voltage of high voltage source 2, the arcing distance that point discharge device 3 and grounding electrode plate are 4.The corona discharge process condition of each embodiment sees Table 1.
(2) carbon nano tube suspension preparation
Getting commercially available CNT places container to mix with dimethylacetylamide in required ratio, then proportion is that the ultrasonic wave of 20kHz carries out ultrasonic concussion, continue about 30min, CNT is fully disperseed in dimethylacetylamide, the suspension that then is mixed with desired concn is for subsequent use.The suspension composition of each embodiment sees Table 2, and the diameter of the Single Walled Carbon Nanotube that adopts is distributed as 0.5～5nm, and the diameter of multi-walled carbon nano-tubes is distributed as 10～20nm, and distribution of lengths is 5～10 μ m.
(3) electrospray deposition of carbon nanotubes
Carbon fiber bundle 1 through Corona discharge Treatment is delivered to the electrostatic precipitation district through conveyer belt 6 with phase same rate (seeing Table 1), the carbon nano tube suspension of above-described embodiment 1～7 preparation through conduit 8 be delivered to be positioned at directly over the carbon fiber 1 and with high voltage source 7 anodal spininess injector 9 cavitys that link to each other, and outpoured with 10ml/h by the every hole of metal kernel small needle tube, the capillary needle bobbin is close to be 100 pin/rice
2, pinhole diameter is 0.8mm.At this moment, by applying a suitable voltage in high voltage source 7, carbon nano tube suspension drops in the atomizing of high-pressure electrostatic effect lower moment, this moment CNT along with the aqueous solvent evaporation under electric field action orientation be implanted in the carbon fiber surface fault of construction, obtain CNT and repair carbon fiber; Apply voltage, deposition distance, deposition and control repairing effect by changing HV generator 7.The electrospray deposition parameter of each embodiment sees Table 3.
(4) CNT is repaired carbon fiber heat treatment
Carbon fiber after the CNT reparation is entered in the annealing device 11 of argon atmosphere in uniform temperature heat treatment, to process zone distance be 6m to available heat in the treating apparatus.Control thermal effectiveness by control heat treatment temperature and processing time (conveyer belt transmission speed sees Table 1).The electrospray deposition parameter of each embodiment sees Table 3.
Measure TENSILE STRENGTH and the tensile strength calculated increase rate of carbon fiber before and after CNT applies, the results are shown in Table 3.
Table 1 carbon fiber electrically corona embodiment technological parameter
Table 2 suspension configuration embodiment
* the weight ratio of Single Walled Carbon Nanotube and multi-walled carbon nano-tubes is 1: 2.
Each embodiment electrospray deposition of table 3, Technology for Heating Processing and effect
Annotate: 1) weight ratio of deposition is carbon fiber: CNT;
2) TENSILE STRENGTH I, TENSILE STRENGTH II are respectively the TENSILE STRENGTH of carbon fiber before and after CNT applies;
3) TENSILE STRENGTH increase rate=[(TENSILE STRENGTH II-TENSILE STRENGTH I)/TENSILE STRENGTH I] * 100%.
Claims (2)
1. method that improves tensile strength of carbon fibers, its adopts and improves electrospray sedimentation CNT is implanted in the surface texture defective of carbon fiber and then increases its intensity, it is characterized in that the method comprises following process:
1) carbon fiber Corona discharge Treatment: the carbon fiber bundle 1 after pre-oxidation, the charing is sent to the high-voltage corona discharge district by conveyer belt 6 carries out Corona discharge Treatment, corona discharge assembly comprises that high voltage source 2, point discharge device 3 and grounding electrode plate 4 form, wherein high voltage source 2 is the negative electricity generator, its negative pole links to each other with point discharge device 3 by wire 21, and is anodal by wire 22 ground connection; By the translational speed 5～30m/h of control conveyer belt 6, the corona voltage of high voltage source 2-5～-30kV, arcing distance (point discharge device 3 and grounding electrode plate 4 spacings) is 1～5cm;
2) carbon nano tube suspension configuration: CNT and organic solvent are mixed with stable homogeneous suspension, organic solvent is a kind of in dimethylacetylamide, dimethyl formamide, oxolane or the ethanol, and the content of CNT is 10～60g/L in the suspension;
3) electrostatic precipitation CNT: the carbon fiber bundle 1 through Corona discharge Treatment enters the electrostatic precipitation district through conveyer belt 6 with identical speed, the electrostatic precipitation device is comprised of high voltage source 7, spininess injector 9 and grounding electrode plate 4 ', high voltage source 7 is positive electric generator, its anodal wire 71 that passes through links to each other with spininess injector 9, and negative pole is by wire 72 ground connection; Carbon nano tube suspension is delivered to spininess injector 9 cavitys that are positioned at directly over the carbon fiber 1 through conduit 8, high voltage source 7 applies voltage 20～50kV and forms the electro-deposition district with grounding electrode plate 4 ', carbon fibre tow 1 lies on conveyer belt 6 and consists of acceptor, carbon nano tube suspension is deposited on CNT in the carbon fiber surface in the surface texture defective by electrostatic atomization, obtains CNT and repairs carbon fiber; Deposition distance (distance between injector syringe needle and the carbon fiber bundle) is controlled to be 5～30cm, and in the weight ratio of carbon fiber and CNT, the deposition of CNT is controlled to be 1000 on the carbon fiber: (0.1～4);
4) CNT is repaired carbon fiber heat treatment: carbon fiber bundle is delivered in the annealing device 11 with identical speed behind the CNT spray deposition, heat-treats 300～1600 ℃ of heat treatment temperatures under inert gas argon gas atmosphere.
2. the method for raising tensile strength of carbon fibers according to claim 1 is characterized in that process 1) described corona voltage-20～-25kV, described arcing distance is 2～3cm, the preferred 10～20m/h of the translational speed of described conveyer belt 6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109137310A (en) * | 2018-10-29 | 2019-01-04 | 浙江康洁丝新材料科技有限公司 | A kind of tow medium spraying mechanism, method and multipurpose elasticizer |
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| JP2011047096A (en) * | 2009-08-27 | 2011-03-10 | Taisei Kaken:Kk | Method for manufacturing fiber and leather containing carbon-based nano structure as metal material having electric conductivity, and product therefrom |
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| CN109137310A (en) * | 2018-10-29 | 2019-01-04 | 浙江康洁丝新材料科技有限公司 | A kind of tow medium spraying mechanism, method and multipurpose elasticizer |
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Application publication date: 20130403 |